ES2397303T3 - Catalyst composition and process for ethylene oligomerization - Google Patents
Catalyst composition and process for ethylene oligomerization Download PDFInfo
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- ES2397303T3 ES2397303T3 ES08855368T ES08855368T ES2397303T3 ES 2397303 T3 ES2397303 T3 ES 2397303T3 ES 08855368 T ES08855368 T ES 08855368T ES 08855368 T ES08855368 T ES 08855368T ES 2397303 T3 ES2397303 T3 ES 2397303T3
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- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
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- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
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Abstract
Composición de catalizador que comprende: (a) un complejo de cromo(II) binuclear; (b) un ligando de la estructura general (A) R1R2P-N(R3)-P(R4)-N(R5)-H o (B) R1R2P-N(R3)-P(R4)-N(R5)-PR6R7, en el que R1, R2, R3, R4, R5, R6 y R7 se seleccionan independientemente entre amino, alquilo C1-C10, arilo y arilo sustituido, en el que la unidad PNPN o PNPNP opcionalmente es parte de un sistema de anillo, en el que al menos uno de los átomos de P o de N de la estructura (A) o de la estructura (B) es un miembro de anillo, estando formado el anillo por uno o varios compuestos constitutivos de las estructuras (A) o (B) por sustitución eliminando formalmente por compuesto constitutivo dos grupos enteros R1-R7 o H, un átomo de cada uno de dos grupos R1-R7, o un grupo entero R1-R7 o H y un átomo de otro grupo R1-R7, y uniendo los sitios de valencia insaturada creados así formalmente por un enlace covalente por compuesto constitutivo para proporcionar la misma valencia que la inicialmente presente en un sitio dado; y (c) un activador o cocatalizadorCatalyst composition comprising: (a) a binuclear chromium (II) complex; (b) a ligand of the general structure (A) R1R2P-N (R3) -P (R4) -N (R5) -H or (B) R1R2P-N (R3) -P (R4) -N (R5) -PR6R7, in which R1, R2, R3, R4, R5, R6 and R7 are independently selected from amino, C1-C10 alkyl, aryl and substituted aryl, in which the PNPN or PNPNP unit is optionally part of a system of ring, in which at least one of the atoms of P or N of the structure (A) or of the structure (B) is a ring member, the ring being formed by one or several constituent compounds of the structures (A ) or (B) by substitution by formally eliminating two whole groups R1-R7 or H, one atom of each of two groups R1-R7, or one whole group R1-R7 or H and one atom of another group R1- R7, and joining the sites of unsaturated valence formally created by a covalent bond by constitutive compound to provide the same valence as initially present at a given site; and (c) an activator or cocatalyst
Description
Composición de catalizador y procedimiento para la oligomerización de etileno Catalyst composition and process for ethylene oligomerization
La presente invención se refiere a una composición de catalizador y a un procedimiento para la oligomerización de etileno. The present invention relates to a catalyst composition and a process for the oligomerization of ethylene.
Las alfa-olefinas lineales (AOL) son intermedios muy útiles para la fabricación de detergentes, lubricantes sintéticos, copolímeros, alcoholes plastificantes y otros muchos productos importantes. Hay varios fabricantes de tales AOL por oligomerización de etileno, por ejemplo, SHELL, BP, SABIC, AMOCO, CHEVRON, PHILIPS, etc. Un problema intrínseco de todos estos procedimientos de oligomerización de etileno catalizada con metales es la producción de mezclas de ALS siguiendo una distribución aritmética (Schultz–Flory o Poisson), que son difíciles de separar y cuya composición con frecuencia no corresponde a la demanda del mercado. Para resolver esta situación técnica y económicamente insatisfactoria, hay un profundo interés en soslayar las limitaciones técnicas y transformar las reacciones de oligomerización de etileno no selectivas en procesos más selectivos. Recientemente, estas actividades se concentran predominantemente en la trimerización selectiva de etileno en 1-hexeno (recapitulación: Linear alpha-olefins (AOL) are very useful intermediates for the manufacture of detergents, synthetic lubricants, copolymers, plasticizer alcohols and many other important products. There are several manufacturers of such AOL by oligomerization of ethylene, for example, SHELL, BP, SABIC, AMOCO, CHEVRON, PHILIPS, etc. An intrinsic problem of all these metal-catalyzed ethylene oligomerization processes is the production of ALS mixtures following an arithmetic distribution (Schultz-Flory or Poisson), which are difficult to separate and whose composition often does not correspond to market demand. . To resolve this technical and economically unsatisfactory situation, there is a deep interest in circumventing technical limitations and transforming non-selective ethylene oligomerization reactions into more selective processes. Recently, these activities are predominantly concentrated in the selective trimerization of ethylene into 1-hexene (recap:
D.H. Morgan y otros, J. Organomet. Chem. 2004, 689, 3641 y referencias citadas en ese trabajo), así como la tetramerización de etileno en 1-octeno (recopilación reciente: D. Wass, Dalton Trans. 2007, 816). D.H. Morgan et al., J. Organomet. Chem. 2004, 689, 3641 and references cited in that work), as well as the tetramerization of ethylene in 1-octene (recent compilation: D. Wass, Dalton Trans. 2007, 816).
Son conocidas varias patentes para la trimerización de etileno en 1-hexeno y la tetramerización de etileno en 1octeno. En la mayoría de estos casos se usaron diferentes precatalizadores de cromo en combinación con una serie ancha de diferentes sistemas de ligando y agentes activadoress (como compuestos de alquilo de metales de un grupo principal). Several patents are known for the trimerization of ethylene in 1-hexene and the tetramerization of ethylene in 1octene. In most of these cases different chromium precatalysts were used in combination with a wide range of different ligand systems and activating agents (such as metal alkyl compounds of a main group).
Son catalizadores de trimerización de etileno basados en cromo de la técnica anterior con compuestos de cromo, activadoress de organoaluminio y diferentes ligandos, los que figuran, por ejemplo, en las siguientes publicaciones de patentes: U.S. 4.668.838; EP 0 668 105; U.S.5.750.817; U.S. 6.031.145; U.S. 5.811.681; EP 537609; EP 1574492; U.S. 2004783429; WO 2005039758; FR 2833191; U.S. 2002035029; WO 2002004119; WO 200183447 y EP 1110930. Aquí se reivindicaron varios ligandos dadores quelantes y no quelantes y un gran número de complejos precursores de Cr(III). En el documento WO 2003004158 se reivindicaron complejos de Cr(II) tales como acetato de cromo (II) junto con ciclopentadienos sustituidos como sistemas de ligando adecuados, además de los complejos de Cr(III) ya descritos y usados. En el documento WO 2003053891 también se reivindican complejos de Cr(II) tales como, por ejemplo, acetato de cromo(II). Los ligandos reivindicados son bis(2-difenilfosfino-etil)aminas y derivados de las mismas. Chromium-based ethylene trimerization catalysts of the prior art with chromium compounds, organoaluminium activators and different ligands, which are listed, for example, in the following patent publications: U.S. 4,668,838; EP 0 668 105; U.S. 5,750,817; U.S. 6,031,145; U.S. 5,811,681; EP 537609; EP 1574492; U.S. 2004783429; WO 2005039758; FR 2833191; U.S. 2002035029; WO 2002004119; WO 200183447 and EP 1110930. Several chelating and non-chelating donor ligands and a large number of Cr (III) precursor complexes were claimed here. In WO 2003004158 Cr (II) complexes such as chromium (II) acetate were claimed together with substituted cyclopentadiennes as suitable ligand systems, in addition to the Cr (III) complexes already described and used. WO 2003053891 also claims Cr (II) complexes such as, for example, chromium (II) acetate. The claimed ligands are bis (2-diphenylphosphino-ethyl) amines and derivatives thereof.
Entre los catalizadores de tetramerización de etileno de la técnica anterior figuran diferentes compuestos de metales de transición, activadoress organoaluminio o diferentes ligandos, que se han usado en la misma forma o en forma ligeramente modificada para el proceso de trimerización. Las patentes concernientes al procedimiento son; patente U.S. 6.184.426; patente U.S. 3.676.523; patente DE 14 43 927; patente U.S. 3.906.053; WO 2005/086251; WO 2006108803; WO 2006099053; WO 2007057455; WO 2007057458 y WO 2007088329. En la mayoría de estas patentes, la mezcla de olefinas obtenida no contiene más del 25 % en peso de 1-octeno. En algunas de las solicitudes más recientes se reivindicaron diferentes ligandos de PNP y similares ligandos dadores quelantes junto con complejos de Cr(II) sólos (WO 2004/056578 y WO 2004/056479). Estas solicitudes fueron las primeras en demostrar que en la oligomerización de etileno se puede alcanzar una alta selectividad a favor de 1-octeno (hasta del 70 % en masa) con simultáneamente una producción de 1-hexeno simultáneamente menor. Se señaló que los sistemas de nueve miembros formados (cromociclononano) son la razón de la tetramerización selectiva de etileno en 1-octeno con una selectividad del 70 % en masa. Among the prior art ethylene tetramerization catalysts are different transition metal compounds, organoaluminium activators or different ligands, which have been used in the same or slightly modified form for the trimerization process. The patents concerning the procedure are; U.S. patent 6,184,426; U.S. patent 3,676,523; DE 14 43 927; U.S. patent 3,906,053; WO 2005/086251; WO 2006108803; WO 2006099053; WO 2007057455; WO 2007057458 and WO 2007088329. In most of these patents, the olefin mixture obtained does not contain more than 25% by weight of 1-octene. In some of the most recent applications different PNP ligands and similar chelating donor ligands were claimed together with Cr (II) complexes alone (WO 2004/056578 and WO 2004/056479). These applications were the first to demonstrate that in the oligomerization of ethylene, high selectivity can be achieved in favor of 1-octene (up to 70% by mass) with simultaneously a simultaneously lower production of 1-hexene. It was noted that the nine-member systems formed (chromocyclononane) are the reason for the selective tetramerization of ethylene in 1-octene with a selectivity of 70% by mass.
El documento US 2006/293546A1 da a conocer como su realización más preferida composiciones de catalizador que comprenden una fuente de cromo, incluidos compuestos y complejos de Cr(II) y Cr(III), mencionando específicamente complejos de Cr binucleares tales como teraquis([eta]-alil)dicromo(II), así como varios carboxilatos de Cr(II), en particular bis(acetato) de cromo(II), un ligando lineal R1R2P-N(R3)-PR4R5, aunque no abarcando los grupos –NHR o –NRP< como cualquiera de R1, R2, R4 o R5, y un activador, siendo el uso contemplada olefina, en particular trimerización y tetramerización de etileno. Para una selección de fuentes específicas de Cr(III) mencionadas y también usadas en los ejemplos de trabajo, se indica que son preferidas éstas por razones de más alta productividad de oligómero. US 2006 / 293546A1 discloses as its most preferred embodiment catalyst compositions comprising a chromium source, including Cr (II) and Cr (III) compounds and complexes, specifically mentioning binuclear Cr complexes such as terachis ([ eta] -alyl) dichrome (II), as well as several carboxylates of Cr (II), in particular chromium (II) bis (acetate), a linear ligand R1R2P-N (R3) -PR4R5, although not encompassing the groups - NHR or -NRP <as any of R1, R2, R4 or R5, and an activator, the olefin contemplated use being, in particular trimerization and tetramerization of ethylene. For a selection of specific sources of Cr (III) mentioned and also used in the working examples, it is indicated that these are preferred for reasons of higher oligomer productivity.
Los catalizadores selectivos de trimerización y tetramerización de etileno y los procedimientos conocidos generalmente tienen que sobrellevar algunos inconvenientes. Los catalizadores presentan sólo bajas selectividades para los productos deseados 1-hexeno y/o 1-octeno debido a los subproductos de los canales de reacciones secundarias. Además, se obtienen purezas limitadas de los productos, esto es, las selectividades dentro del corte específico de C6 o C8 debido a isomerización, formación de olefinas ramificadas, etc. También se detecta la formación de cera, esto es, formación de productos pesados de cadena larga de un número alto de carbonos. Esto es también cierto para la formación de polímeros (polietileno, polietileno ramificado y/o reticulado), lo que conduce a una pérdida considerable del rendimiento de producto y al ensuciamiento del equipo. Además se ha de mencionar que los procedimientos de la técnica anterior sólo presentan unos giros de proceso bajos, resultando cara la actividad catalítica por kg de producto. Usualmente, la preparación de los catalizadores y ligandos de la técnica anterior es cara. Los ligandos usualmente son difíciles de sintetizar, lo que da por resultado una disponibilidad Selective trimerization and tetramerization catalysts of ethylene and known processes generally have to overcome some drawbacks. The catalysts have only low selectivities for the desired products 1-hexene and / or 1-octene due to by-products of the secondary reaction channels. In addition, limited purities of the products are obtained, that is, the selectivities within the specific C6 or C8 cut due to isomerization, branched olefin formation, etc. The formation of wax is also detected, that is, formation of heavy long-chain products of a high number of carbons. This is also true for the formation of polymers (polyethylene, branched and / or crosslinked polyethylene), which leads to a considerable loss of product yield and fouling of the equipment. In addition, it should be mentioned that the prior art procedures only have low process turns, the catalytic activity being expensive per kg of product. Usually, the preparation of the prior art catalysts and ligands is expensive. Ligands are usually difficult to synthesize, which results in availability.
5 deficiente y un alto coste del catalizador. El comportamiento del catalizador es muy susceptible a rastros de impurezas y con frecuencia los componentes del catalizador son de difícil manipulación en un medio técnico. Los procedimientos de la técnica anterior usualmente requieren condiciones de reacción duras, esto es, altas temperaturas y presiones, lo que da por resultado alta inversión, costes de mantenimiento y energía altos. Finalmente, se han de esperar altos costes para cocatalizador/activador. 5 poor and high catalyst cost. The behavior of the catalyst is very susceptible to traces of impurities and often the catalyst components are difficult to handle in a technical environment. Prior art procedures usually require harsh reaction conditions, that is, high temperatures and pressures, resulting in high investment, high maintenance costs and energy. Finally, high costs for cocatalyst / activator have to be expected.
10 Es por tanto un objetivo de la presente invención soslayar las dificultades de la técnica anterior y proporcionar una composición de catalizador que tenga selectividades y purezas mejoradas en la oligomerización de etileno sin formación de ceras o polímero, presentando mejores giros de proceso con costes satisfactorios para preparar el catalizador y el ligando. It is therefore an objective of the present invention to overcome the difficulties of the prior art and to provide a catalyst composition having improved selectivities and purities in the oligomerization of ethylene without wax or polymer formation, presenting better process turns with satisfactory costs for Prepare the catalyst and ligand.
Además se proporciona un procedimiento para la oligomerización de etileno. In addition, a process for oligomerization of ethylene is provided.
15 El primer objetivo se alcanza con una composición de catalizador que comprende: (a) un complejo de cromo(II) binuclear; (b) un ligando de la estructura general (A) R1R2P-NR3)-P(R4)-NR5)-H o (B) R1R2P-N(R3)-P(R4)-N(R4)-PR6R7, en los que R1, R2, R3, R4, R5, R6 y R7 se seleccionan independientemente entre alquilo C1-10, arilo y arilo sustituido y siendo la unidad PNPN- o PNPNP opcionalmente parte de un sistema de anillo, y (c) un activador o cocatalizador. The first objective is achieved with a catalyst composition comprising: (a) a binuclear chromium (II) complex; (b) a ligand of the general structure (A) R1R2P-NR3) -P (R4) -NR5) -H or (B) R1R2P-N (R3) -P (R4) -N (R4) -PR6R7, in which R1, R2, R3, R4, R5, R6 and R7 are independently selected from C1-10 alkyl, aryl and substituted aryl and the PNPN- or PNPNP unit is optionally part of a ring system, and (c) an activator or cocatalyst.
20 Se ha de entender que como ligando se puede usar cualesquier derivados cíclicos de (A) y (B), siendo miembro de anillo al menos uno de los átomos P o N de la unidad PNPN (estructura (A)) o unidad PNPNP (estructura (B)), estando formado el anillo por uno o varios compuestos constituyentes de las estructuras (A) o (B) por sustitución, esto es, eliminando formalmente por compuesto constitutivo dos grupos enteros (R1-R2) (según se define), o un grupo entero R1-7 (según se define), o H y un átomo de otro grupo R1-7 (según se define), y uniendo formalmente los It is to be understood that as a ligand any cyclic derivatives of (A) and (B) can be used, at least one of the P or N atoms of the PNPN unit (structure (A)) or PNPNP unit being ring member ( structure (B)), the ring being formed by one or several constituent compounds of structures (A) or (B) by substitution, that is, formally eliminating two whole groups (R1-R2) by constitutive compound (as defined) , or an entire group R1-7 (as defined), or H and an atom of another group R1-7 (as defined), and formally joining the
25 sitios insaturados en valencia formalmente así creados por un enlace covalente por compuesto constitutivo para proporcionar la misma valencia inicialmente presente en un sitio dado. 25 formally unsaturated sites in Valencia thus created by a covalent bond per constitutive compound to provide the same valence initially present at a given site.
Preferiblemente, el complejo de cobre tiene un enlace Cr-Cr o dos centros de cromo están conectados mediante un ligando puente. Preferably, the copper complex has a Cr-Cr bond or two chromium centers are connected by a bridge ligand.
Muy preferiblemente, el complejo binuclear de cromo se selecciona entre: En una realización, R1, R2, R3, R4, R5, R6 y R7 se seleccionan entre cloro, amino, trimetilsililo, metilo, etilo, isopropilo, t-butilo, fenilo, bencilo, tolilo y xililo. Most preferably, the binuclear chromium complex is selected from: In one embodiment, R1, R2, R3, R4, R5, R6 and R7 are selected from chlorine, amino, trimethylsilyl, methyl, ethyl, isopropyl, t-butyl, phenyl, benzyl, tolyl and xylyl.
En otra realización, el activador o el cocatalizador se seleccionan entre trimetilaluminio, trietilaluminio, 5 triisopropilaluminio, triisobutilaluminio, sesquicloruro de etilaluminio, cloruro de dietilaluminio, dicloruro de etilaluminio, metilaluminoxano (MAO) o mezclas de los mismos. In another embodiment, the activator or cocatalyst is selected from trimethylaluminum, triethylaluminum, triisopropyl aluminum, triisobutylaluminum, ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane (MAO) or mixtures thereof.
El ligando se puede seleccionar entre (Ph)2P-Ni(i-Pr)-(P)(CH3)-N(i-Pr) H, (Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H, (Ph)2P-N(iPr)-P(Ph)-N(Ph)-H, (Ph)2P-N(i-Pr)-P(Ph)-N(t-butil)-H y (Ph)2P-N(i-Pr)-P(PhN(CH(CH3)(PH))-H. The ligand can be selected from (Ph) 2P-Ni (i-Pr) - (P) (CH3) -N (i-Pr) H, (Ph) 2P-N (i-Pr) -P (Ph) - N (i-Pr) -H, (Ph) 2P-N (iPr) -P (Ph) -N (Ph) -H, (Ph) 2P-N (i-Pr) -P (Ph) -N ( t-butyl) -H and (Ph) 2P-N (i-Pr) -P (PhN (CH (CH3) (PH)) - H.
Preferiblemente, la composición de catalizador comprende un disolvente, que se puede seleccionar entre Preferably, the catalyst composition comprises a solvent, which can be selected from
10 hidrocarburos aromáticos, hidrocarburos alifáticos de cadena lineal y cíclicos, olefinas de cadena lineal y éteres, preferiblemente tolueno, benceno, etilbenceno, cumeno, xilenos, mesitileno, hexano, octano, ciclohexano, metilciclohexano, hexeno, hepteno, octeno, dietil éter o tetrahidrofurano o mezclas de los mismos. Muy preferiblemente tolueno. 10 aromatic hydrocarbons, aliphatic linear and cyclic hydrocarbons, linear chain olefins and ethers, preferably toluene, benzene, ethylbenzene, cumene, xylenes, mesitylene, hexane, octane, cyclohexane, methylcyclohexane, hexene, heptene, octene, diethyl ether or tetrahydride or mixtures thereof. Very preferably toluene.
Un segundo objetivo de la invención se alcanza por un procedimiento para la oligomerización de etileno, que comprende someter una composición de catalizador de acuerdo con la invención a una fase gaseosa de etileno en un reactor y realizar una oligomerización. A second objective of the invention is achieved by a process for the oligomerization of ethylene, which comprises subjecting a catalyst composition according to the invention to a gaseous phase of ethylene in a reactor and performing oligomerization.
Preferiblemente, la oligomerización se lleva a cabo a una presión de 100 a 20.000 kPa, preferiblemente de 1.000 a Preferably, the oligomerization is carried out at a pressure of 100 to 20,000 kPa, preferably 1,000 to
También preferiblemente, la oligomerización se realiza a temperatura ambiente o de 10 a 200 ºC, preferiblemente de 20 a 100 ºC. Also preferably, the oligomerization is carried out at room temperature or from 10 to 200 ° C, preferably from 20 to 100 ° C.
En una realización, el proceso se realiza continuamente, semicontinuamente o discontinuamente. In one embodiment, the process is carried out continuously, semicontinuously or discontinuously.
El tiempo medio de permanencia es de 10 minutos a 20 horas, preferiblemente de 1 a 4 horas. The average residence time is 10 minutes to 20 hours, preferably 1 to 4 hours.
Muy preferiblemente, el proceso es la trimerización o tetramerización. Most preferably, the process is trimerization or tetramerization.
Se ha encontrado sorprendentemente que un procedimiento para la oligomerización de etileno usando la composición de catalizador inventiva evita el amplio espectro de compuestos de AOL y permite la producción selectiva de los productos económicamente más deseados, esto es, 1-hexeno y 1-octeno. Sin que haya precedentes, se consiguen selectividad, pureza y frecuencia de giro de proceso altas. It has been surprisingly found that a process for the oligomerization of ethylene using the inventive catalyst composition avoids the broad spectrum of AOL compounds and allows the selective production of the most economically desired products, that is, 1-hexene and 1-octene. Without precedents, high process selectivity, purity and frequency of rotation are achieved.
La presente invención está basada en el hecho de que la tetramerización de etileno en 1-octeno y la trimerización de etileno en 1-hexeno pueden transcurrir más eficientemente usando un complejo de metal de transición binuclear en vez de un complejo de metal de transición mononuclear, cuyo mecanismo involucra metalociclononanos y metalacilheptanos, respectivamente. The present invention is based on the fact that the tetramerization of ethylene in 1-octene and the trimerization of ethylene in 1-hexene can proceed more efficiently using a binuclear transition metal complex instead of a mononuclear transition metal complex, whose mechanism involves metallocyclonanes and metallacylheptans, respectively.
Se asume, sin que ello suponga adherirse a teoría alguna, que para los complejos de cromo binuclear usados en la reacción de tetramerización se sugiere un mecanismo en el que la reacción transcurre a través de metalociclopentanos que dimerizan la cadena C4 en una cadena saturada C8 entre centros metálicos como se olustra en el siguiente esquema: It is assumed, without implying any theory, that for the binuclear chromium complexes used in the tetramerization reaction, a mechanism is suggested in which the reaction proceeds through metallocyclopentanes that dimerize the C4 chain in a C8 saturated chain between metal centers as illustrated in the following scheme:
Este mecanismo se caracteriza por el nuevo principio de una eliminación dinuclear reductora de cromo(II) a través de cromo(I) a cromo() que conduce a 1-octeno. This mechanism is characterized by the new principle of a reductive dinuclear removal of chromium (II) through chromium (I) to chromium () leading to 1-octene.
La composición de catalizador de acuerdo con la presente invención se puede sintonizar por ligandos adecuados al nuevo principio de eliminación dinuclear reductora de cromo(0) a través de cromo a cromo(0) (caso: ligandos neutros) o de cromo(I)/(II) a través de cromo(II)/(I) a cromo (I)/(0) (caso: ligandos aniónicos), lo que conduce selectivamente a 1-hexeno. The catalyst composition according to the present invention can be tuned by ligands suitable to the new principle of chromium reducing dinuclear elimination (0) through chromium to chromium (0) (case: neutral ligands) or chromium (I) / (II) through chromium (II) / (I) to chromium (I) / (0) (case: anionic ligands), which selectively leads to 1-hexene.
Adicionalmente, se encontró sorprendentemente que la modificación de un ligando tridentado, tal como (fenil)2PN(isopropil)-P(fenilo)2 por una unidad adicional NH(isopropilo) dio por resultado el ligando tetradentado ((fenil)2PN(isopropil)P(fenil)NH(isopropilo)). El uso del primer ligando en la composición de catalizador dio por resultado una alta selectividad a favor de la tetramerización de etileno, mientras que el último ligando dio por resultado una alta selectividad a favor de la trimerización o la tetramerización de etileno dependiendo de los sustituyentes, como se demostrará más adelante en la sección de ejemplos. Additionally, it was surprisingly found that modification of a tridentate ligand, such as (phenyl) 2PN (isopropyl) -P (phenyl) 2 by an additional unit NH (isopropyl) resulted in the tetradentate ligand ((phenyl) 2PN (isopropyl) P (phenyl) NH (isopropyl)). The use of the first ligand in the catalyst composition resulted in high selectivity in favor of ethylene tetramerization, while the last ligand resulted in high selectivity in favor of trimerization or tetramerization of ethylene depending on the substituents, as will be demonstrated later in the examples section.
Con otras palabras, el procedimiento inventivo da por resultado la producción de 1-octeno y 1-hexeno con un giro de proceso alto y una alta selectividad. Se puede obtener un cambio fácil de la producción de 1-octeno a 1-hexeno usando ligandos específicos. Además se obtiene una alta reproductibilidad, por ejemplo, el sistema de catalizador es estable frente a la interferencia de impurezas y fluctuaciones en las condiciones de proceso. La formación de ceras y polímeros queda satisfactoriamente suprimida. Además, en el procedimiento inventivo se pueden emplear condiciones de reacción suaves, por lo que consecuentemente los costes inventivos son bajos para una planta a escala técnica y bajos los costes de energía y operativos. In other words, the inventive process results in the production of 1-octene and 1-hexene with a high process spin and high selectivity. An easy change in the production of 1-octene to 1-hexene can be obtained using specific ligands. In addition, high reproducibility is obtained, for example, the catalyst system is stable against interference from impurities and fluctuations in process conditions. The formation of waxes and polymers is satisfactorily suppressed. In addition, mild reaction conditions can be used in the inventive process, whereby consequently the inventive costs are low for a plant on a technical scale and low the energy and operational costs.
Un ligando a usar en la composición inventiva de catalizador es puede preparar como sigue: A ligand to be used in the inventive catalyst composition is can be prepared as follows:
Preparación de Ph2PN(i-Pr)PMeNH(i-Pr): Se añadieron lentamente 2,21 g de Ph2PCl (10 mmol) a una mezcla de 1,62 g de MeP(NH)(i-Pr)2 (10 mmol) (Eur. J. Inorg. Chem. 1999, 12, 2355-68)y 5 ml de trietilamina en 15 ml de tolueno a 0 ºC. La solución se agitó durante 2 h más a t.a. y luego se filtró para eliminar el hidrocloruro de amina. Después de evaporar los compuestos volátiles en vacío quedó un aceite pegajoso. Rendimiento: 80 %. Preparation of Ph2PN (i-Pr) PMeNH (i-Pr): 2.21 g of Ph2PCl (10 mmol) was slowly added to a mixture of 1.62 g of MeP (NH) (i-Pr) 2 (10 mmol ) (Eur. J. Inorg. Chem. 1999, 12, 2355-68) and 5 ml of triethylamine in 15 ml of toluene at 0 ° C. The solution was stirred for a further 2 h at t.a. and then filtered to remove amine hydrochloride. After evaporating the volatile compounds in vacuo a sticky oil remained. Yield: 80%.
RMN 31P (C6D6): 33,7, 57,6 (ancha). 31P NMR (C6D6): 33.7, 57.6 (wide).
Trimerización por complejos binucleares: Trimerization by binuclear complexes:
Ejemplo 1: Trimerización de etileno usando {[(i-Pr)2N]Cr[ -(i-Pr)2N]}2, ((fenil)2PN(isopropil)P(fenil)NH(isopropilo)) y trietilaluminio Example 1: Trimerization of ethylene using {[(i-Pr) 2N] Cr [ - (i-Pr) 2N]} 2, ((phenyl) 2PN (isopropyl) P (phenyl) NH (isopropyl)) and triethylaluminum
Un reactor a presión de 300 ml, equipado con tubo de inmersión, vaina termoprotectora, agitador con arrastre de gas, espiral de refrigeración y unidades de control de la temperatura, presión y velocidad del agitador (todo conectado a un sistema de adquisición de datos) se purgó con argón seco para hacerlo inerte y luego se llenó con 100 ml de tolueno anhidro. Luego se combinaron 81,7 mg (0,2 mol) de ((fenil) 2PN(isopropil)P(fenil)NH(isopropilo) en 10 ml de tolueno con 65,6 mg de {[(i-Pr)2N]Cr[ -(i-Pr)2N]} (0,13 mmol) bajo capa de argón. La solución de catalizador se pasó al reactor bajo corriente constante de argón junto con 3,6 ml de una solución 1,9 M de trietilaluminio en tolueno. Se cerró el reactor, se puso a 3.000 kPa de presión con etileno seco y se calentó a 50 ºC. Mientras que se agitaba a 1200 rpm, se controló el consumo de etileno con el sistema de adquisición de datos y una balanza electrónica por pesada continua del cilindro de presión de etileno. Después de un tiempo de permanencia de 120 min, se apagó la reacción en la fase líquida transfiriendo el líquido inventivo, mediante la presión de etileno, a un recipiente de vidrio llenado con aproximadamente 100 ml de agua. Se cuantificó mediante un gasímetro calibrado la totalidad de fase gaseosa del espacio de cabecera del reactor y luego fue recogido cuantitativamente en una bolsa para gas purgada y evacuada. A pressure reactor of 300 ml, equipped with immersion tube, thermoprotective sheath, agitator with gas drag, cooling spiral and control units of the temperature, pressure and speed of the agitator (all connected to a data acquisition system) it was purged with dry argon to make it inert and then filled with 100 ml of anhydrous toluene. Then 81.7 mg (0.2 mol) of ((phenyl) were combined 2PN (isopropyl) P (phenyl) NH (isopropyl) in 10 ml of toluene with 65.6 mg of {[(i-Pr) 2N] Cr [- (i-Pr) 2N]} (0.13 mmol) low argon cape The catalyst solution was passed to the reactor under a constant argon stream together with 3.6 ml of a 1.9 M solution of triethylaluminum in toluene. The reactor was closed, placed at 3,000 kPa pressure with dry ethylene and heated to 50 ° C. While stirring at 1200 rpm, ethylene consumption was controlled with the data acquisition system and an electronic balance by continuous weighing of the ethylene pressure cylinder. After a residence time of 120 min, the reaction was quenched in the liquid phase by transferring the inventive liquid, by means of ethylene pressure, to a glass vessel filled with approximately 100 ml of water. The entire gas phase of the reactor header space was quantified by means of a calibrated gas meter and then quantitatively collected in a bag for purged and evacuated gas.
Después de separar la fase orgánica líquida, se determinó la masa total por pesada. Posteriormente se analizó separadamente por CG/FID. Sobre la base de los datos medidos, se concluyó el balance de masas y se determinaron los rendimientos y selectividades globales. En la Tabla 1 se resume la distribución del producto de este ejemplo. After separating the liquid organic phase, the total mass was determined by weighing. It was subsequently analyzed separately by CG / FID. On the basis of the measured data, the mass balance was concluded and the overall yields and selectivities were determined. Table 1 summarizes the product distribution of this example.
Ejemplo comparativo 2: Trimerización de etileno usando CrCl3(tetrahidrofurano)3, ((fenil)2PN(isopropil)P(fenil)NH(isopropilo)) y trietilaluminio Comparative Example 2: Trimerization of ethylene using CrCl3 (tetrahydrofuran) 3, ((phenyl) 2PN (isopropyl) P (phenyl) NH (isopropyl)) and triethylaluminum
De modo análogo al Ejemplo 1, se llenó un reactor a presión de 300 ml con 100 ml de tolueno anhidro. Una solución de 81,7 mg (0.13 mmol) de ((fenil)2PN(isopropil)-P(fenil)NH(isopropilo)) en 10 ml de tolueno se combinó con 50,0 mg (0,13 mmol) de CrCl3(tetrahidrofurano)3 bajo capa de argón. La solución de catalizador se pasó al reactor junto con 3,6 ml de una solución 1,9 M de trietilaluminio en tolueno. Se cerró el reactor y se sometió a una presión de 3.000 kPa de etileno seco y se calentó a 50 ºC. Después de un tiempo de permanencia de 120 min mientras que se agitaba a 1200 rpm, la mezcla de reacción se trató y analizó como se ha indicado antes. En la Tabla 1 se resume la distribución del producto de este ejemplo.Similarly to Example 1, a 300 ml pressure reactor was filled with 100 ml of anhydrous toluene. A solution of 81.7 mg (0.13 mmol) of ((phenyl) 2PN (isopropyl) -P (phenyl) NH (isopropyl)) in 10 ml of toluene was combined with 50.0 mg (0.13 mmol) of CrCl3 (tetrahydrofuran) 3 under argon layer. The catalyst solution was passed to the reactor together with 3.6 ml of a 1.9 M solution of triethylaluminum in toluene. The reactor was closed and subjected to a pressure of 3,000 kPa of dry ethylene and heated to 50 ° C. After a residence time of 120 min while stirring at 1200 rpm, the reaction mixture was treated and analyzed as indicated above. Table 1 summarizes the product distribution of this example.
Tabla 1. Tandas de trimerización de etileno Table 1. Ethylene trimerization batches
- Ejemplo Example
- Actividad, kg prod./g Cr Rend. de C6, % en peso Rend. de C8, % en peso 1-hex en C6 Activity, kg prod./g Cr Yield of C6,% by weight Yield of C8,% by weight 1-hex in C6
- 1 2 1 2
- 145 34 88 89 1 1 99,0 99,0 145 34 88 89 eleven 99.0 99.0
Ejemplo 3: Tetramerización usando {[(i-Pr)2N]Cr[ -(i-Pr)2N]}2, ((fenil)2PN(isopropil)P(metil)NH(isopropilo)) y trietilaluminio Example 3: Tetramerization using {[(i-Pr) 2N] Cr [ - (i-Pr) 2N]} 2, ((phenyl) 2PN (isopropyl) P (methyl) NH (isopropyl)) and triethylaluminum
De modo análogo al Ejemplo 1, se llenó un reactor a presión de 300 ml con 100 ml de tolueno anhidro y una solución de 69,3 mg de ((fenil) 2PN(isopropil)-P(metil)NH(isopropilo)) (0,2 mmol) en 10 ml de tolueno junto con 65,6 mg de {[(i-Pr)2N]Cr[ -(i-Pr)2N]} (0,13 mmol) Después de añadir 3,6 ml de una solución 1,9 M de trietilaluminio en tolueno, se cerró el reactor y se sometió a una presión de 3.000 kPa de etileno seco y se calentó a 50 ºC. Después de un tiempo de permanencia de 120 min mientras que se agitaba a 1200 rpm, la mezcla de reacción se trató y analizó como se ha indicado antes. En la Tabla 2 se resume la distribución del producto de este ejemplo. Similarly to Example 1, a 300 ml pressure reactor was filled with 100 ml of anhydrous toluene and a solution of 69.3 mg of ((phenyl) 2PN (isopropyl) -P (methyl) NH (isopropyl)) (0.2 mmol) in 10 ml of toluene together with 65.6 mg of {[(i-Pr) 2N] Cr [- (i-Pr) 2N ]} (0.13 mmol) After adding 3.6 ml of a 1.9 M solution of triethylaluminum in toluene, the reactor was closed and subjected to a pressure of 3,000 kPa of dry ethylene and heated to 50 ° C. After a residence time of 120 min while stirring at 1200 rpm, the reaction mixture was treated and analyzed as indicated above. Table 2 summarizes the product distribution of this example.
Ejemplo comparativo 4: Oligomerización de etileno usando CrCl3(tetrahidrofurano)3, ((fenil)2PN(isopropil)5 P(metil)NH(isopropilo)) y trietilaluminio Comparative Example 4: Oligomerization of ethylene using CrCl3 (tetrahydrofuran) 3, ((phenyl) 2PN (isopropyl) 5 P (methyl) NH (isopropyl)) and triethylaluminum
De modo análogo al Ejemplo 1, se llenó un reactor a presión de 300 ml con 100 ml de tolueno anhidro y una solución de 69,3 mg de ((fenil)2PN(isopropil)-P(metil)NH(isopropilo)) (0,2 mmol) en 10 ml de tolueno junto con 50,5 mg de CrCl3(tetrahidrofurano)3 (0,13 mmol). Después de añadir 3,6 ml de una solución 1,9 M de trietilalumiio en tolueno, se cerró el reactor y se sometió a una presión de 3.000 kPa de etileno seco y se calentó a 50 ºC. Después Similarly to Example 1, a 300 ml pressure reactor was filled with 100 ml of anhydrous toluene and a solution of 69.3 mg of ((phenyl) 2PN (isopropyl) -P (methyl) NH (isopropyl)) ( 0.2 mmol) in 10 ml of toluene together with 50.5 mg of CrCl3 (tetrahydrofuran) 3 (0.13 mmol). After adding 3.6 ml of a 1.9 M solution of triethylaluminum in toluene, the reactor was closed and subjected to a pressure of 3,000 kPa of dry ethylene and heated to 50 ° C. After
10 de un tiempo de permanencia de 120 min mientras que se agitaba a 1200 rpm, la mezcla de reacción se trató y analizó como se ha indicado antes. La distribución del producto de este ejemplo es invariable respecto a una distribución de Schulz-Flory y se resume en la Tabla. 10 of a residence time of 120 min while stirring at 1200 rpm, the reaction mixture was treated and analyzed as indicated above. The product distribution of this example is invariable with respect to a Schulz-Flory distribution and is summarized in the Table.
Tabla 2. Tandas de tetramerización de etileno Table 2. Ethylene tetramerization batches
- Ejemplo Example
- Actividad, kg prod/g de Cr Rend. de C6, % en peso Rend. de C8, % en peso 1-hex en C6 1-oct en C8 Activity, kg prod / g of Cr Yield of C6,% by weight Yield of C8,% by weight 1-hex in C6 Oct 1 at C8
- 3 4 3. 4
- 21 33 8 30 82 28 98,0 98.0 98,0 98,0 21 33 8 30 82 28 98.0 98.0 98.0 98.0
Como se puede deducir de los ejemplos, cambiando el ligando usado en la composición del catalizador usado se puede lograr pasar fácilmente de trimerización (Ejemplos 1 y 2) a tetramerización (Ejemplo 3). Además, usando complejos binucleares de cromo (II) es posible pasar fácilmente de oligomerización no selectiva (Ejemplo 4) a tetramerización (Ejemplo 3) As can be deduced from the examples, changing the ligand used in the composition of the catalyst used can easily be achieved from trimerization (Examples 1 and 2) to tetramerization (Example 3). In addition, using binuclear chromium (II) complexes it is possible to easily go from non-selective oligomerization (Example 4) to tetramerization (Example 3)
Claims (12)
- 2. 2.
- Composición de catalizador de acuerdo con la reivindicación 1, en la que el complejo de cromo tiene un enlace Cr-Cr o dos centros de cromo están conectados mediante un ligando puente. Catalyst composition according to claim 1, wherein the chromium complex has a Cr-Cr bond or two chromium centers are connected by a bridge ligand.
- 3. 3.
- Composición de catalizador de acuerdo con cualquiera de las reivindicaciones precedentes, en la que el complejo de cromo binuclear se selecciona entre: Catalyst composition according to any of the preceding claims, wherein the binuclear chromium complex is selected from:
- 8.8.
- Composición de catalizador de acuerdo con la reivindicación 7, en la que el disolvente se selecciona entre hidrocarburos aromáticos, hidrocarburos alifáticos de cadena lineal y cíclicos. olefinas de cadena lineal y éteres. Catalyst composition according to claim 7, wherein the solvent is selected from aromatic hydrocarbons, straight chain and cyclic aliphatic hydrocarbons. linear chain olefins and ethers.
- 9. 9.
- Procedimiento para la oligomerización de etileno, que comprende someter una composición de catalizador de acuerdo con cualquiera de las reivindicaciones 1 a 8 a una fase gaseosa de etileno en un reactor y realizar una oligomerización a una temperatura de 20 a 100 ºC. Process for the oligomerization of ethylene, which comprises subjecting a catalyst composition according to any one of claims 1 to 8 to a gas phase of ethylene in a reactor and performing an oligomerization at a temperature of 20 to 100 ° C.
- 10. 10.
- Procedimiento de acuerdo con la reivindicación 9 en el que la oligomerización se realiza a una presión de 100 a Process according to claim 9 wherein the oligomerization is performed at a pressure of 100 to
- 11. eleven.
- Procedimiento de acuerdo con la reivindicación 9 o 10, procedimiento que se realiza de manera continua. Procedure according to claim 9 or 10, a procedure that is carried out continuously.
- 12. 12.
- Procedimiento de acuerdo con cualquiera de las reivindicaciones 9 a 11, en el que el tiempo medio de permanencia es de 10 minutos a 20 horas. Method according to any of claims 9 to 11, wherein the average residence time is 10 minutes to 20 hours.
- (b) (b)
- un ligando de la estructura general a ligand of the general structure
- (A)(TO)
- R1R2P-N(R3)-P(R4)-N(R5)-H o R1R2P-N (R3) -P (R4) -N (R5) -H or
- (B)(B)
- R1R2P-N(R3)-P(R4)-N(R5)-PR6R7, R1R2P-N (R3) -P (R4) -N (R5) -PR6R7,
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| ES2371218T3 (en) * | 2009-04-09 | 2011-12-28 | Saudi Basic Industries Corporation | COMPOSITION OF CATALYST AND PROCEDURE FOR THE OLIGOMERIZATION OF ETHYLENE. |
| EP2354113A1 (en) | 2010-02-04 | 2011-08-10 | Linde AG | Method for deactivation of a catalyst |
| EP2489431B1 (en) | 2011-02-16 | 2013-05-01 | Linde AG | Method for preparing a catalyst composition for oligomerization of ethylene and respective catalyst composition pre-formation unit |
| KR102088445B1 (en) | 2012-05-09 | 2020-03-13 | 사솔 테크날러지 (프로프라이어터리) 리미티드 | Oligomerisation of olefinic compounds with reduced polymer formation |
| KR101579880B1 (en) | 2012-05-10 | 2016-01-04 | 주식회사 엘지화학 | Process for oligomerization of ethylene |
| EP2684857A1 (en) | 2012-07-10 | 2014-01-15 | Saudi Basic Industries Corporation | Method for oligomerization of ethylene |
| CN112246285A (en) * | 2014-02-03 | 2021-01-22 | 沙特基础工业公司 | Catalyst composition pre-forming unit for preparing a catalyst composition for the oligomerization of ethylene |
| CN106573236B (en) * | 2014-07-24 | 2020-05-29 | 沙特基础工业全球技术有限公司 | Catalyst composition and process for oligomerization of ethylene to produce 1-hexene and/or 1-octene |
| KR101757369B1 (en) | 2014-12-11 | 2017-07-12 | 주식회사 엘지화학 | Ligand compound, organic chromium compound, catalyst system for oligomerization of olefins and method for oligomerization of olefins using the catalyst system |
| KR101757370B1 (en) | 2015-06-01 | 2017-07-12 | 주식회사 엘지화학 | 1-Octene composition |
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| US20100298618A1 (en) | 2010-11-25 |
| TWI440503B (en) | 2014-06-11 |
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| US8778827B2 (en) | 2014-07-15 |
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| BRPI0819904A2 (en) | 2015-09-15 |
| RU2467797C2 (en) | 2012-11-27 |
| MY150515A (en) | 2014-01-30 |
| CN101855015A (en) | 2010-10-06 |
| CA2703021C (en) | 2015-01-20 |
| MX2010005266A (en) | 2010-06-02 |
| KR101445431B1 (en) | 2014-09-26 |
| TW200942327A (en) | 2009-10-16 |
| RU2010126183A (en) | 2012-01-10 |
| BRPI0819904B1 (en) | 2018-02-06 |
| CA2703021A1 (en) | 2009-06-04 |
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